Adsorption of Zn(II) from aqueous solution and separation of zinc isotopes by displacement chromatography using chelating adsorbent.

The removal of zinc ions (Zn(II)) in water and the separation of zinc isotopes were fully investigated in this study. Imidodiacetic acid (IDA) type adsorbent (named PSGI) based on polystyrene spheres (PS) was synthesized by simultaneous irradiation grafting. By adsorption method, the removal of Zn(II) from water by the chelating adsorbent was studied in batch experiments. Under optimized condition, PSGI showed the removal efficiency of more than 98 % for Zn(II) and the adsorption capacity of 70.1 mg/g. Langmuir isothermal and pseudo-second-order kinetic model fitted the experimental results better, indicating that the adsorption is dominated by chemical adsorption. The spent adsorbent (PSGI-Zn) was used for further zinc isotope separation by displacement chromatography using EDTA-NH4 solution as eluent. Due to the mass effect of isotopes, 70Zn was found to preferentially fractionated into the front-end effluents with the highest front enrichment values of 70Zn/64Zn. By extending the migration distance to 20 m, we obtained the best isotope enrichment with the front maximum enrichment values as 1.0949, 1.0739 and separation coefficient values as 1.977 × 10-3, 8.33 × 10-3 corresponding to the isotope pairs 66Zn/64Zn, 68Zn/64Zn.

Effects of endodontic irrigation solutions on structural, chemical, and mechanical properties of coronal dentin: A scoping review.

OBJECTIVE: This review aims to assess structural, chemical, and mechanical properties of coronal dentin after endodontic irrigation. MATERIALS AND METHODS: Reporting followed the PRISMA extension for scoping reviews. An electronic search was carried out in PubMed, Embase, and Cochrane Library. Records filtered by language and published up to November 4, 2022 were independently screened by two researchers. Studies evaluating structural, chemical, or mechanical properties of human permanent coronal dentin after irrigation within the scope of nonsurgical root canal treatment were included. Data were extracted regarding study type, sample description and size, experimental groups, outcome, evaluation method, and main findings. RESULTS: From the initial 1916 studies, and by adding 2 cross-references, 11 in vitro studies were included. Seven studies provide ultrastructural and/or chemical characterization, and six assessed microhardness and/or flexural strength. One percent to 8% sodium hypochlorite (NaOCl) and 1%-17% ethylenediaminetetraacetic acid (EDTA) were the most commonly tested solutions, with contact times of 2-240 min (NaOCl) and 1-1440 min (EDTA) being evaluated. CONCLUSIONS: Overall, the literature is consensual regarding the inevitable impact of NaOCl and chelating agents on coronal dentin, with both deproteinizing and decalcifying effects being concentration- and time-dependent. The alteration of mechanical parameters further confirmed the surface and subsurface ultrastructural and chemical changes. CLINICAL SIGNIFICANCE: Endodontic treatment success highly depends on restorative sealing. Understanding the result of exposing coronal dentin, the main substrate for bonding, to irrigants' action is crucial. The deproteinizing and decalcifying effects of NaOCl and chelating agents are both concentration- and time-dependent, causing surface and subsurface ultrastructural, chemical, and mechanical alterations.

Comparative Evaluation of the Effect of Different Chelating Agents on Mineral Content and Erosion of Radicular Dentine: A FESEM-EDS Analysis.

OBJECTIVE: Irrigating solutions play an important role in the debridement and disinfection of the root canal space, and thus, it is crucial to comprehend their effects on the composition and surface structure of radicular dentine. This study evaluated and compared the effects of 17% ethylenediaminetetraacetic acid (EDTA), 9% 1-hydroxyethylidene-1,1-bisphosphonate (HEBP) and 0.2% chitosan on the mineral content and erosion of radicular dentine when used as a final rinse. METHODS: Sixty extracted human mandibular premolar teeth were decoronated and instrumented to ProTaper size F2. After final instrumentation, the samples were randomly divided into 4 groups (n=15) according to the type of final irrigant used: Normal saline (control), 17% EDTA, 9% HEBP and 0.2% chitosan. Field emission scanning electron microscopy was used to assess the erosion of radicular dentine, and energy dispersive X- ray spectroscopy was used to quantify the radicular dentine mineral composition at the coronal, middle and apical levels of all the prepared samples after final irrigation. The one-way analysis of variance was used for intra-group and inter-group comparisons of means, the Kruskal Wallis test for intra-group and inter-group comparisons of medians and Tukey's post hoc test for pairwise comparisons. RESULTS: There was no significant difference in the levels of calcium (Ca), phosphorus (P) and Ca/P ratio after final rinse with 17% EDTA, 9% HEBP and 0.2% chitosan at all three root levels (p>0.05); except at the coronal level, where 0.2% chitosan caused significantly less alteration in Ca levels and Ca/P ratio than 17% EDTA and 9% HEBP respectively (p<0.05). 17% EDTA, 9% HEBP and 0.2% chitosan caused no erosion at the middle and apical levels. Meanwhile, 17% EDTA and 9% HEBP caused moderate erosion at the coronal level. CONCLUSION: Alternatives to 17% EDTA during final irrigation can be 9% HEBP and 0.2% chitosan. (EEJ-2023-06-078).

Direct analysis of biodegradable chelating agents based on liquid chromatography/electrospray ionization mass spectrometry using a metal-free hydrophilic interaction liquid chromatographic column.

Recently, biodegradable aminopolycarboxylic acid chelating agents have attracted attention as an alternative to environmentally persistent chelating agents such as ethylenediamine-N,N,N',N'-tetraacetic acid. However, the detection of chelating agents requires complexation with metals or derivatization by esterification reagents, and their direct detection using the currently available analytical methods still represents a challenge. Herein, we describe a direct analytical method for the biodegradable chelating agents ethylenediamine-N,N'-disuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, methylglycine-N,N'-diacetic acid, and N,N-bis(carboxymethyl)-L-glutamic acid, via ultra-performance liquid chromatography/electrospray ionization quadrupole/time-of-flight mass spectrometry. Satisfactory retention and separation with a good peak shape were successfully achieved using a metal-free hydrophilic interaction liquid chromatographic column. The calibration curves showed good linearity in the range of 1.0-50 µM with correlation coefficients greater than 0.9988. The detection limits ranged from 0.04 to 0.12 µM. Furthermore, the developed method could be applied to the quantitative analysis of the four chelating agents in biodegradation and photodegradation experiments at the laboratory level. The proposed method, which offers the advantages of quickness, sensitivity, and requiring no complicated pretreatment steps, is expected to contribute significantly to the practical analysis of chelating agents in environmental water samples.

Evaluation of the effects of different chelation agents on root dentin roughness.

Successful root canal treatment requires effective irrigation of the entire root canal system. While chelating agents support irrigation, they can also alter physicochemical properties of the root dentin structure. The aim of this study is to evaluate the effect of different chelation agents on root dentin roughness. Twenty-five extracted maxillary incisors were used in this study. Samples were separated longitudinally and divided into five groups: distilled water, NaOCl, ethylenediaminetetraacetic acid (EDTA), phytic acid and citric acid (CA). Atomic force microscope and energy dispersive X-ray spectroscopy analyses were used for analysing. One-way analysis of variance and Turkey tests were used in the statistical analysis of the study. EDTA, CA and phytic acid solutions increased the roughness and phytic acid and CA solutions decreased the Ca/P ratio in dentin tissue. No statistical difference was observed in the other groups. The decrease of Ca/P ratio should be taken under consideration during irrigation. The increase in surface roughness may provide clinical benefit by supporting the adhesion of the root canal filling materials to the dentin surface.

Ferrous sulfate efficiently kills Vibrio parahaemolyticus and protects salmon sashimi from its contamination.

The primary seafood-borne pathogen Vibrio parahaemolyticus seriously threats the health of consumers preferring raw-fish products, becoming a global concern in food safety. In the present study, we found ferrous sulfate (FeSO4), a nutritional iron supplement, could efficiently induce the death of V. parahaemolyticus. Further, the bactericidal mechanisms of FeSO4 were explored. With a fluorescent probe of Fe2+, a significant influx of Fe2+ was determined in V. parahaemolyticus exposed to FeSO4, and the addition of an intracellular Fe2+ chelator was able to block the cell death. This suggested that cell death in V. parahaemolyticus induced by FeSO4 was dependent on the influx of Fe2+. It was intriguing that we did not observe the eruption of reactive oxygen species (ROS) and lipid hydroperoxides by Fe2+, but the application of liproxstatin-1 (a ferroptosis inhibitor) significantly modified the occurrence of cell death in V. parahaemolyticus. These results suggested FeSO4-induced cell death in V. parahaemolyticus be a ferroptosis differing from that in mammalian cells. Through transcriptome analysis, it was discovered that the exposure of FeSO4 disturbed considerable amounts of gene expression in V. parahaemolyticus including those involved in protein metabolism, amide biosynthesis, two-component system, amino acid degradation, carbon metabolism, citrate cycle, pyruvate metabolism, oxidative phosphorylation, and so on. These data suggested that FeSO4 was a pleiotropic antimicrobial agent against V. parahaemolyticus. Notably, FeSO4 was able to eliminate V. parahaemolyticus in salmon sashimi as well, without affecting the color, texture, shearing force, and sensory characteristics of salmon sashimi. Taken together, our results deciphered a unique ferroptosis in V. parahaemolyticus by FeSO4, and highlighted its potential in raw-fish products to control V. parahaemolyticus.

Consequences of zinc deficiency on zinc localization, taurine transport, and zinc transporters in rat retina.

The colocalization of taurine and zinc transporters (TAUT, ZnTs) has not been explored in retina. Our objective is to evaluate the effect of the intracellular zinc chelator N,N,N,N-tetrakis-(2-pyridylmethyl) ethylenediamine (TPEN) on zinc localization and colocalization TAUT and ZnT-1 (of plasma membrane), 3 (vesicular), and 7 (vesicular and golgi apparatus) in layers of retina by immunohistochemistry. To mark zinc, it was used cell-permeable fluorescent Zinquin ethyl ester. Specific first and secondary antibodies, conjugated with rhodamine or fluorescein-isothiocyanate were used to mark TAUT and ZnTs. The fluorescence results were reported as integrated optical density (IOD). Zinc was detected in all layers of the retina. The treatment with TPEN produced changes in the distribution of zinc in layers of retina less in the outer nuclear layer compared with the control. TAUT was detected in all layers of retina and TPEN chelator produced decrease of IOD in all layers of retina except in the photoreceptor compared with the control. ZnT 1, 3, and 7 were distributed in all retina layers, with more intensity in ganglion cell layer (GCL) and in the layers where there is synaptic connection. For all transporters, the treatment with TPEN produced significant decrease of IOD in layers of retina least in the inner nuclear layer for ZnT1, in the photoreceptor for ZnT3 and in the GCL and outer plexiform layer for ZnT7. The distribution of zinc, TAUT, and ZnTs in the layers of retina is indicative of the interaction of taurine and zinc for the function of the retina and normal operation of said layers. HIGHLIGHTS: Taurine and zinc are two molecules highly concentrated in the retina and with relevant functions in this structure. Maintaining zinc homeostasis in this tissue is necessary for the normal function of the taurine system in the retina. The study of the taurine transporter and the different zinc transporters in the retina (responsible for maintaining adequate levels of taurine and zinc) is relevant and novel, since it is indicative of the interactions between both molecules in this structure.

Sequential injection method for bi-parametric determination of iron and manganese in soil leachates.

The aim of this work was to develop a sequential injection (SI) method for the determination of the micronutrients iron and manganese, in soil leachates, as a tool to assess potential groundwater contamination. The described sequential injection method was based on the reaction of iron with chelator MRB12, a greener alternative chromogenic reagent, and the reaction of manganese with zincon, within a single manifold. The developed SI method enabled the determination of iron in the range 0.10-1.00 mg L-1, and manganese in the range 0.25-2.5 mg L-1 with a limit of detection of 0.08 mg L-1 for iron and 0.24 mg L-1 for manganese. The determination of both parameters was made in 6 minutes, in triplicate. The application to monitor laboratory scale soil core columns (LSSCs), as a simulation of the soil leaching process, proved its efficiency to assess potential contamination of ground waters. Iron and manganese contents were effectively analysed in two different scenarios to mimic the leaching process with rainwater and fertilizer.

Effects of the chelating agent DTPA on naturally accumulating metals in the body.

Diethylenetriaminepentaacetate (DTPA) is the most widely used chelating agent for Pu and Am. Volunteers were assigned to receive intravenous injections or aerosol inhalations of 1 g of DTPA on days 1-4; volunteers received once daily injections of CaDTPA or ZnDTPA, CaDTPA inhalation as an aerosol, or CaDTPA injection on day 1 and ZnDTPA on days 2-4. CaDTPA injection or inhalation increased the excretion rates of Zn in urine with concomitantly reduced levels of serum Zn. Injection of CaDTPA reduced activities of serum alkaline phosphatase (AP) in parallel with the kinetics of Zn, whereas CaDTPA and ZnDTPA injection reduced activities of lactate dehydrogenase (LDH), and reduced activities of creatinine kinase (CK) were observed upon CaDTPA injection and its inhalation. Intravenous administration of CaDTPA and ZnDTPA enhanced excretion rates of Mn in urine, whereas transient reduction of Mn levels in serum was detected only via CaDTPA injection. Both CaDTPA and ZnDTPA transiently reduced levels of Mg in serum without affecting the excretion rates. On the other hand, both DTPAs increased excretion rates of toxic metals such as Pb and Cd, and CaDTPA also increased the rates of Hg. These results suggest that DTPA, and especially CaDTPA, removes essential metals and that the activities of these metalloenzymes are good indicators for the imbalance of essential metals during the DTPA administration. Our results also show that CaDTPA injection is more potent for removing these metals than ZnDTPA and inhalation of CaDTPA, and DTPA may be useful for the treatment of acute heavy metal poisoning with Pb, Cd, or Hg.

Multivalent cation and polycation polymer preparations influence pharmacokinetics of dolutegravir via chelation-type drug interactions.

Dolutegravir (DTG) is an integrase inhibitor, whose gastrointestinal absorption is impaired by the formation of chelates with multivalent metal cation preparations. However, little is known regarding the interactions of DTG with preparations containing other multivalent metal cations or with polycation polymer preparations. This study examined how the pharmacokinetics of DTG are affected by co-administration with Al(OH)3, LaCO3, and the polycation polymers bixalomer (Bxl) and sevelamer (Svl). Prior to oral administration of DTG (5 mg/kg), rats were orally administered Al(OH)3 (150 or 300 mg/kg), LaCO3 (50 or 75 mg/kg), Bxl (250 or 500 mg/kg), or Svl (300 or 600 mg/kg). Serum concentrations of DTG were then measured over the next 24 h. Compared to the administration of DTG alone, its co-administration with Al(OH)3, LaCO3, Bxl, and Svl led to reduced serum concentration of DTG, and consequently, a significantly reduced area under the curve. These comparisons also revealed a considerable reduction in the maximum concentration, suggesting that the interactions of these agents with DTG in the intestinal tract inhibit absorption of DTG. The above results demonstrate that Al(OH)3, LaCO3, Bxl, and Svl affect the pharmacokinetics of DTG and indicate the need for caution when combining any of the above preparations with DTG.

Comparison between different sources of minerals in horses with nutritional secondary hyperparathyroidism / [Comparação entre diferentes fontes de minerais em cavalos com hiperparatireoidismo secundário nutricional]

Minerals perform several functions in the body, such as coagulation actions, muscle contraction, enzymatic and hormonal production, among others. This study aims to evaluate the effect of a 150 days chelated and not chelated mineral supplementation with and without potassium oxalate on serological parameters and bone mineral density of horses. Twenty-four crossbred yearlings (12 females and 12 males) with an average age of 21±3 months and body weight of 330.8±37.9kg were divided into four groups containing six equines in each (three females and three males) in a completely randomized design with repeated measurements in a 2x2 factorial arrangement. Treatments were: 1 - chelated minerals compound; 2 - chelated minerals compound and potassium oxalate; 3 - not chelated minerals compound; and 4 - not chelated minerals compound and potassium oxalate. Clinical signs of nutritional secondary hyperparathyroidism (NSH) were observed only in treatment 4. Results showed no treatment effect in bone biopsy for calcium, phosphorus and bone density. There were significant reductions of parathyroid hormone (PTH) means concentrations in treatments 2 and 4 during supplementation. Animals supplemented with chelated minerals compounds avoided mineral imbalances and NSH even when in dietary potassium oxalate challenged.(AU)

Os minerais desempenham diversas funções no organismo, como ações de coagulação, contração muscular, produção enzimática e hormonal, entre outras. O objetivo deste estudo foi avaliar o efeito da suplementação de minerais quelatados e não quelatados, por 150 dias, com e sem oxalato de potássio, sobre parâmetros sorológicos e densidade mineral óssea em equinos. Vinte e quatro filhotes mestiços (12 fêmeas e 12 machos), com idade média de 21±3 meses e peso corporal de 330,8±37,9kg, foram divididos em quatro grupos contendo seis equinos cada (três fêmeas e três machos), em delineamento inteiramente ao acaso, com repetição medida em arranjo fatorial 2x2. Os tratamentos foram: 1 - composto mineral quelatado; 2 - composto mineral quelatado e oxalato de potássio; 3 - composto mineral não quelatado; e 4 - composto mineral não quelatado e oxalato de potássio. Os sinais clínicos do hiperparatireoidismo secundário nutricional (NSH) foram observados apenas no tratamento 4. Os resultados não mostraram efeito de tratamento na biópsia óssea para cálcio, fósforo e densidade óssea. Houve redução significativa do hormônio da paratireoide (PTH) em concentrações médias nos tratamentos 2 e 4 durante a suplementação. Os animais suplementados com compostos minerais quelatados evitaram desequilíbrios minerais e NSH, mesmo quando desafiados no oxalato de potássio na dieta.(AU)

Self-assembling nitrilotriacetic acid nanofibers for tracking and enriching His-tagged proteins in living cells.

Specific and expeditious identification and enrichment of target proteins in living cells is often a challenging task. The hexahistidine (6His) tag is frequently used to label artificially engineered proteins produced in prokaryotic or eukaryotic cells. Utilizing the interaction between 6His-tag and nitrilotriacetic acid (NTA) mediated by divalent metal ions (Ni2+, Cu2+, Zn2+ or Co2+), we designed and synthesized a series of Nap-G/Biotin/ANA-FFpYGK-NTA probes that, assisted by alkaline phosphatase (ALP), self-assemble into nanofibers. The probe consists of an NTA group that specifically binds to 6His-tag, an FFpY group that promotes self-assembly facilitated by ALP, and a hydrophobic (Nap-G/ANA/Biotin) capping group for various applications. We demonstrate that the ANA-FFpYGK-NTA(Ni2+) nanofibers are fit for real-time tracking of His-tagged protein in living cells, and the Biotin-FFpYGK-NTA(Ni2+) nanofibers are for isolating His-tagged proteins and other proteins that they interact with.

Quantification of endospores in ancient permafrost using time-resolved terbium luminescence.

We describe herein a simple procedure for quantifying endospore abundances in ancient and organic-rich permafrost. We repeatedly (10x) extracted and fractionated permafrost using a tandem filter assembly composed of 3 and 0.2 µm filters. Then, the 0.2 µm filter was washed (7x), autoclaved, and the contents eluted, including dipicolinic acid (DPA). Time-resolved luminescence using Tb(EDTA) yielded a LOD of 1.46 nM DPA (6.55 × 103 endospores/mL). In review, DPA/endospore abundances were ~2.2-fold greater in older 33 ky permafrost (258 ± 36 pmol DPA gdw-1; 1.15 × 106 ± 0.16 × 106 spores gdw-1) versus younger 19 ky permafrost (p = 0.007297). This suggests that dormancy increases with permafrost age.

Complete genome sequence of Micromonospora craniellae LHW63014T, a potential metal ion-chelating agent producer.

Micromonospora craniellae LHW63014T is a novel marine Micromonospora, isolated from a Craniella species sponge collected in the South China Sea. In this study, we report the complete genome sequence of M. craniellae LHW63014T, which is comprised of a circular chromosome of 6,839,926 bp with the G + C content of 70.9 mol%. The complete genome contained 6572 protein-coding genes, 48 tRNA genes, and 9 rRNA genes. Genomic annotations revealed that 79.09% of the protein-coding genes were assigned to the COG database, among which, the abundant genes were predicted to be involved in transcription, replication, recombination and repair, and amino acid transport and metabolism. Secondary metabolites prediction using antiSMASH revealed that 22 biosynthetic gene clusters (BGC) of secondary metabolites were located in the genome of M. craniellae LHW63014T, 19 of which showed low similarity (<50%) to known BGCs and 5 of which showed the closest homology with BGCs encoding metal ion-chelating agents, indicating the immense potential of M. craniellae LHW63014T to produce a wide variety of novel antibiotics, especially for metal ion-chelating agents.

Physicochemical properties of skim milk powder dispersions prepared with calcium-chelating sodium tripolyphosphate, trisodium citrate, and sodium hexametaphosphate.

Due to health benefits of proteins, the demand for protein beverages has grown rapidly. Translucent protein drinks with neutral pH may have advantages over acidic beverages that may cause dental erosion, and skim milk powder (SMP) is an affordable protein ingredient. Dissociating casein micelles by calcium chelators is a well-known method to reduce SMP dispersion turbidity, but much is to be studied for physicochemical properties as affected by chelator type and concentration. The objective of the present study was to characterize physicochemical properties of dispersions with 5% (wt/vol) SMP after addition of 0 to 30 mM sodium tripolyphosphate, trisodium citrate, or sodium hexametaphosphate. The turbidity was decreased with increasing chelator concentration, with the lowest turbidity observed in the SMP dispersions with sodium hexametaphosphate. The smallest hydrodynamic diameter was observed at an intermediate chelator concentration, resulting from the balance of casein micelle dissociation and aggregation of dissociated caseins induced at an elevated ionic strength. Heating at 90°C for 5 min increased turbidity but lowered hydrodynamic diameter of SMP dispersions, with some exceptions. The morphology of SMP dispersions differed for each chelator and was also affected by chelator concentration and heating. Trisodium citrate was the most effective to demineralize colloidal calcium phosphate in casein micelles, but the amount of dissolved calcium was not directly correlated with the decreased turbidity, indicating different chelating mechanisms by each chelator. Analysis of serum calcium and phosphorus concentrations also suggested that the type and concentration of soluble and insoluble calcium phosphates and their partitioning in the serum and casein micelles were dynamically changed by the studied parameters to affect dispersion turbidity and structures of casein micelles. Findings from the present study may be used to formulate translucent beverages incorporating SMP and other casein micelle ingredients.

Bio-properties of Saba banana (Musa 'saba', ABB Group): Influence of maturity and changes during simulated in vitro gastrointestinal digestion.

Saba banana, a popular fruit crop grown in Southeast Asia, is an economical source of a variety of beneficial agents. This study examined the variations in total phenolic, flavonoid, and antioxidant activities of five maturity stages of Saba banana, and their changes during simulated in vitro gastrointestinal digestion as affected by varying structural compositions. Antioxidant activities were evaluated using ferric reducing antioxidant power (FRAP), metal ion chelating (MIC) activity, and 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) assays. Results of DPPH and ABTS were compared in terms of TEAC (Trolox Equivalent Antioxidant Capacity) and VCEAC (Vitamin C Equivalent Antioxidant Capacity) values. Bio-properties were found to be highest in mature green stage with values slightly decreased as ripening proceeded. Simulated digestion showed a continuous increase in total phenolic with comparatively faster release in structure-less state (slurry) than samples with intact structure (cut). The trend of antioxidant activities was increased in the gastric phase and then decreased at the onset of intestinal phase, except for MIC which showed a reverse effect. Our study indicated that the bio-properties of Saba banana were affected by maturity and modifications in its physical structure and composition could influence the release behaviors of food components during simulated digestion.

Impacts of a shallow shipwreck on a coral reef: A case study from St. Brandon's Atoll, Mauritius, Indian Ocean.

Shallow shipwrecks, can have severe ecological and toxicological impacts on coral atolls. In 2012, a tuna longliner ran aground on the reef crest of St Brandon's Atoll, Mauritius, broke up into three pieces which was moved by currents and storms into the lagoon. In the months following the grounding, the coral around the wreck became dead and black. Down-current from the wreck, a dense bloom of filamentous algae (Ulva sp.) attached to coral occurred. To determine the ecological effects of the wreck on the system, the marine biota around the wreck, in the algal bloom, and fish reference zones were counted in 2014. Metal concentrations in reference and affected coral was determined using inductively coupled plasma mass spectrometry (ICP/MS). A pronounced difference was seen in the metal concentration pattern between coral from the wreck- and algal zones, and the coral reference zone. While the wreck zone contained the highest abundance of fish, the fish reference zone had the highest species diversity but with fewer fish. We also counted eleven Critically Endangered hawksbill sea turtles Eretmochelys imbricata and significantly more sea cucumbers in the algal zone than the reference zones. The effects of shipwrecks on coral reefs must be considered a threat over periods of years and should be studied further.

Post-column detection of cadmium chelators by high-performance liquid chromatography using 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid.

Cd(II) is toxic to many species, including humans, because it inactivates a number of enzymes and induces cytopathic effects in the liver, kidney, and skeletal tissues in humans. Metallothionein and glutathione (GSH) play a major role in the protection against Cd(II)-induced toxicity in mammalian cells. In this study, a relatively simple method for detecting trace amounts of Cd(II) chelators was developed by using 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid (TPPS). The TPPS-Cd(II) complex was added to the elutions of high-performance liquid chromatography. The Cd(II) chelators separated by column chromatography were mixed with Cd(II)-bound TPPS (TPPS-Cd(II)). Cd(II) from TPPS-Cd(II) was chelated by the eluted Cd(II) chelators, resulting in the formation of free TPPS. The absorbance of TPPS shifted from 434 nm (TPPS-Cd(II)) to 414 nm (TPPS), and this characteristic shift was used to estimate the quantity and affinity of the Cd(II) chelators. This new method was compared with the bathocuproine disulfonate (BCS) method developed in our previous study. Instead of BCS-Cu(I), TPPS-Cd(II) was used as the colorimetric reagent. The experimental setup of the TPPS-based method is more general, and the preparation of the colorimetric solution is also much simpler than the BCS method. To verify the efficacy of this new method, we determined the actual Cd(II)-chelating ability of GSH in horse blood; the obtained concentration was in good agreement with the previously reported value.

Effects of titanium contamination caused by iron-free high-performance liquid chromatography systems on peak shape and retention of drugs with chelating properties.

Iron-free HPLC systems, better known as biocompatible systems, are generally regarded to be chemically more inert compared to conventional HPLC systems. In this work, we studied the chromatographic behavior of some classes of compounds of pharmaceutical interest, analyzed with iron-free systems. Issues typically associated with metal contamination, i.e. strong peak tailing, were observed when using an amide polar-embedded column. Effects of the contamination were visible when anhydrous methanol-acetonitrile was used, indicating that this solvent, albeit generally considered safe for conventional HPLC systems, induce corrosion of iron-free systems. The confirmation of titanium as main acting contaminant came from systematically studying the contribution of each wetted component of the HPLC system on peak shape of affected molecules. Quantification of titanium by ICP-MS analysis of effluents provided further evidence on the source of contamination. A mechanistic description of the complex interaction between titanium ions, organic molecules, and column stationary phase is proposed. In the perspective of developing methods that are fully portable between stainless steel and titanium systems, recommendations are given in terms of potentially sensitive molecules, suitable mobile phase conditions, and type of column to be used.

Secondary Metabolites and Antioxidant Capacity of the Tunisian Lichen Diploschistes ocellatus (Ascomycota).

This study, the first to assess the total phenolic, flavonoid, tannins, and proanthocyanidin content of the Tunisian lichen Diploschistes ocellatus, determined the antioxidant capacity in scavenging 2,2 diphenyl-1-picrylhydrazyl (DPPH), as well as the ferric-reducing and iron-chelating powers. The phenolic compound content of D. ocellatus was shown to be related to antioxidant activity. The highest phenolic and flavonoid contents of extracts were obtained with acetone (286.3 µg GAE/g DW and 3.24 µg CE/g DW, respectively), while the highest tannin and proanthocyanidin contents were obtained with methanol (5.5 µg TAE/g DW and 35.12 µg CE/g DW, respectively). The highest DPPH' scavenging capacity and iron-chelating power of extracts were obtained with methanol (concentration providing 50% inhibition [IC50] = 0.029 mg/mL and IC50 = 0.425 mg/mL, respectively), while acetone extracts showed a higher reducing power (IC50 = 0.118 mg/mL).